SYNTHESIS OF C-ALPHA-ALPHA-UNSYMMETRICALLY DISUBSTITUTED NITROESTERS BY ELECTRON-TRANSFER C-ALKYLATION OF ETHYL 2-NITROPROPIONATE ANION

The ethyl 2-nitropropionate anion was shown to react with six reductiv e alkylating agents to give new C-alpha alpha-unsymmctrically disubsti tuted nitroesters and in some cases new ethyl monosubstituted methacry lates. The C-alkylation was shown to proceed by the S(RN)1 mechanism w hich was confirmed by the classical criteria for S(RN)1 reaction: the electron-withdrawing group effect and classical inhibition experiments by dioxygen, p-dinitrobenzene, cupric chloride or TEMPO. For example, ethyl 2-methyl-2-nitro-3-p-nitrophenylpropionate was transformed in t he corresponding amino acid. (C) 1998 Elsevier Science Ltd. All rights reserved.